CN114988356B - Device and method for preparing hydrogen and oxygen by electron irradiation of liquid water - Google Patents
Device and method for preparing hydrogen and oxygen by electron irradiation of liquid water Download PDFInfo
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- CN114988356B CN114988356B CN202210611241.4A CN202210611241A CN114988356B CN 114988356 B CN114988356 B CN 114988356B CN 202210611241 A CN202210611241 A CN 202210611241A CN 114988356 B CN114988356 B CN 114988356B
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract
The invention discloses a device and a method for preparing hydrogen and oxygen by electron irradiation of liquid water, comprising an electron source chamber and a reaction chamber, which are isolated by a metal film with high melting point; a cathode, an insulating core transformer, a rectifying filter, an accelerator and a metal film serving as an anode are arranged in the electron source chamber; the reaction chamber is internally provided with a gas collecting cathode, a gas collecting anode, a hydrogen separation chamber and an oxygen separation chamber, wherein the gas collecting anode and the gas collecting cathode are connected with the anode and the cathode of a direct current power supply DC; compared with the traditional method and device, the method has a plurality of advantages, does not need catalyst, solute, water vaporization and auxiliary carrier gas, and has the advantages of energy source and reactor separation, stability, safety and the like. The method is novel and has not been reported. The invention has good practical value, provides a sustainable route for converting rich water and energy resources into hydrogen in a synergic way, and can also provide reference for the hydrogenation and gasification of fossil fuels.
Description
Technical Field
The invention belongs to the technical field of high voltage, and relates to a device and a method for preparing hydrogen and oxygen by electron irradiation of liquid water.
Background
The global hydrogen production today is about 7000 ten thousand tons/year. Wherein 50% of the hydrogen was used for the synthesis of ammonia (NH 3 ) This is an extremely important fertilizer and source of fertilizer. 15% hydrogen is used for other chemicals such as hydrochloric acid and the like. Other industrial uses of hydrogen are: synthesis of glycollic acid, as a protective or reducing atmosphere in the metallurgical, semiconductor and lamp manufacturing industries, catalytic hydrogenation in edible oil production, and the like. Hydrogen is also an increasingly important fuel as a method of storing and transporting energy for use in rockets and vehicles to convert hydrogen into electricity by fuel cells.
There are a variety of routes for the production of hydrogen. Most of the hydrogen produced worldwide is produced by methane (CH) 4 ) Steam reforming (SMR) produces, which results in 10 million tons of carbon dioxide emissions per year. Worldwide fossil fuels have carbon dioxide emissions approaching 360 billion tons, 25% of which come from electricity and heat generation, 20% from industry, and 20% from traffic. Due to the link between global warming and carbon dioxide emissions, fossil fuels on earth are increasingly difficult to scale upThe energy crisis formed by the acquisition and gradual exhaustion, and people start to utilize renewable energy sources such as solar energy, wind energy and the like to prepare hydrogen from water.
At present, three methods of an electrolysis method, a photodecomposition method and a plasma discharge method are mainly used for preparing hydrogen from water.
The electricity consumption for hydrogen production by water electrolysis is very high, and the electricity consumption for producing 1 kg of hydrogen is 60kWh. The current electrolytic efficiency of hydrogen production by water electrolysis is about 50-70% due to the influence of solution and external loop resistance. In view of economy and technology, the electricity price of renewable energy sources is reduced to 0.14 yuan/kwh or less, and the overall solar energy to hydrogen (STH) efficiency is 30%, water electrolysis is competitive. Research in more detail has shown that such low cost electricity prices are available only for a small fraction of the time of day when stepped electricity prices are implemented. Thus, economies suggest that the electrolytic cell needs to be connected to the grid to operate for 24 hours, which means that other renewable energy sources need to be integrated into the photovoltaic grid in order to produce hydrogen from water without discharging carbon dioxide.
In photocatalytic water hydrogen production, many semiconductor photocatalysts do not have a proper forbidden bandwidth, or the photon yield is not high, or the energy band position of the conduction band or valence band of the semiconductor is not matched with the reduction potential and oxidation potential of water; the problems of the life of photo-generated electron and hole pairs, the speed of the reduction reaction of the surface of the catalyst, the strength of the water reverse reaction generated by hydrogen and oxygen and the like are all needed to be solved.
The research of hydrogen production by plasma water is still in a preliminary exploration stage, and industrialization is still a distance. Hydrogen production in the case of steam requires energy consumption for liquid water gasification. The discharge ionization hydrogen production in liquid water has not been possible because the average energy of electrons formed during the in-water streamer discharge is estimated to be 0.5-2eV, which is much lower than the gas phase discharge where the electron energy is as high as 10 eV. Most of the research is carried out under the condition of Ar carrier gas, the collision of excited Ar and water molecules dissociates water more effectively to produce hydrogen, the decomposing speed of the argon is improved, but the loss and recycling of the argon increase the hydrogen production cost. Degradation of the blocking medium during discharge remains of concern. With a single blocking medium, electrodes within the reactor corrode, wear and their products during discharge have an effect on hydrogen production and collection. Most importantly, the plasma discharge water hydrogen production is problematic in that the power supply can not separately drive other positive and negative ions to consume electric energy when accelerating electrons, so that the efficiency of the plasma discharge water hydrogen production is a problem.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a device and a method for preparing hydrogen and oxygen by electron irradiation of liquid water.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
in a first aspect, the invention discloses a device for preparing hydrogen and oxygen by electron irradiation of liquid water, comprising:
an electron source chamber in which a cathode is disposed; the electron source chamber is arranged on the reaction chamber and is communicated with the reaction chamber through the metal film; an accelerator for accelerating electrons is arranged between the cathode and the metal film serving as the anode; the cathode and the accelerator are connected with a low-voltage alternating current power supply;
the reaction chamber is internally provided with a gas collecting cathode, a gas collecting anode, a hydrogen separation chamber and an oxygen separation chamber; the gas collecting anode and the gas collecting cathode are respectively connected to the anode and the cathode of the direct current power supply; the hydrogen separation chamber is arranged above the gas collecting cathode, and the oxygen separation chamber is arranged above the gas collecting anode; the hydrogen separation chamber and the oxygen separation chamber are respectively connected with a hydrogen collection system and an oxygen collection system.
The device is further improved in that:
the anode and the accelerator are connected with a low-voltage alternating current power supply through an insulating core transformer and a rectifying filter.
The insulating core transformer and the rectifying filter are arranged in the electron source chamber, and the low-voltage alternating current power supply is arranged outside the electron source chamber.
The anode is of an indirect type and is made of lanthanum hexaboride.
And the electron source chamber is also connected with a vacuum system for maintaining the vacuum degree in the electron source chamber.
The hydrogen collection system comprises a first compressor and a hydrogen tank connected to the outlet of the first compressor, and a hydrogen detection chamber is further connected to the inlet pipeline of the first compressor.
The oxygen collection system comprises a second compressor and an oxygen tank connected to the outlet of the second compressor, and an oxygen detection chamber is further connected to the inlet pipeline of the second compressor.
The reaction chamber is provided with a water inlet and a water outlet, the water inlet is sequentially connected with a first water valve, a first water pump and a reservoir, and an inlet of the reservoir is connected with the water outlet of the reaction chamber.
The reservoir is provided with a water supplementing port, and the water supplementing port is sequentially connected with a second water valve, a second water pump and a reservoir.
In a second aspect, the invention discloses a method for preparing hydrogen and oxygen by electron irradiation of liquid water, comprising the following steps:
step 1, starting a power supply of a vacuum system, and pumping an electron source chamber to an ultrahigh vacuum state;
step 2, opening a first water valve, starting a first water pump, and enabling water to circularly flow through the reaction chamber;
step 3, turning on a direct current power supply, and forming an electrostatic field by a gas collecting anode and a gas collecting cathode of the reaction chamber;
step 4, starting a low-voltage alternating current power supply, boosting, rectifying and filtering by an insulating core transformer and a rectifying filter, supplying power to the accelerator, heating the cathode, and emitting electron beams under a strong electric field between the high-temperature cathode and the accelerator; the electron beam penetrates through the metal film to enter the reaction chamber after being accelerated by the accelerator;
step 5, the liquid water transmitted into the electron beam bombardment reaction chamber generates hydrogen, hydrogen ions, oxygen and oxygen ions; the electrostatic field between the gas collecting cathode and the gas collecting anode enables positive ions such as hydrogen ions to move to the gas collecting cathode to obtain electrons so as to form hydrogen, and enables negative ions such as oxygen ions to move to the gas collecting anode to release electrons so as to form oxygen; the hydrogen separation chamber and the oxygen separation chamber separate hydrogen and oxygen from the mixed gas, respectively.
Compared with the prior art, the invention has the following beneficial effects:
compared with the traditional method and device, the method has a plurality of advantages, does not need catalyst, solute, water vaporization and auxiliary carrier gas, and has the advantages of energy source and reactor separation, stability, safety and the like. The method is novel and has not been reported. The invention has good practical value, provides a sustainable route for converting rich water and energy resources into hydrogen in a synergic way, and can also provide reference for the hydrogenation and gasification of fossil fuels.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of the principle of hydrogen production by water electrolysis.
Fig. 2 is a schematic view of solar photolytic water.
Fig. 3 is a schematic diagram of plasma discharge decomposing water.
FIG. 4 is a schematic diagram of an apparatus for preparing hydrogen and oxygen by electron irradiation of liquid water according to the present invention.
Wherein: 1-anode, 2-cathode, 3-DC power supply, 4-membrane, 5-hydrogen outlet, 6-oxygen outlet, 7-DC bias power supply, 8-electrolyte, 9-high frequency power supply, 10-electrode a, 11-electrode B, 12-blocking medium, 13-steam and argon/helium inlet, 14-hydrogen, oxygen, argon/helium and other gas outlets, 15-plasma discharge zone, 16-electron source chamber, 17-reaction chamber, 18-metal film, 19-cathode, 20-insulated core transformer and rectifying filter, 21-accelerator, 22-low voltage ac power supply, 23-gas collecting cathode, 24-gas collecting anode, 25-hydrogen separation chamber, 26-oxygen separation chamber, 27-first compressor, 28-hydrogen tank, 29-hydrogen detection chamber, 30-second compressor, 31-oxygen tank, 32-oxygen detection chamber, 33-water inlet, 34-first water valve, 35-first water pump, 36-water reservoir, 37-water inlet, 38-second water pump, 39-water outlet, 40-DC power supply, 41-DC power supply, 42-DC bias power supply, 1-DC bias power supply.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that: like reference numerals and letters denote like items in the following figures, and thus once an item is defined in one figure, no further definition or explanation thereof is necessary in the following figures.
In the description of the embodiments of the present invention, it should be noted that, if the terms "upper," "lower," "horizontal," "inner," and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, or the azimuth or the positional relationship in which the inventive product is conventionally put in use, it is merely for convenience of describing the present invention and simplifying the description, and does not indicate or imply that the apparatus or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used merely to distinguish between descriptions and should not be construed as indicating or implying relative importance.
Furthermore, the term "horizontal" if present does not mean that the component is required to be absolutely horizontal, but may be slightly inclined. As "horizontal" merely means that its direction is more horizontal than "vertical", and does not mean that the structure must be perfectly horizontal, but may be slightly inclined.
In the description of the embodiments of the present invention, it should also be noted that, unless explicitly specified and limited otherwise, the terms "disposed," "mounted," "connected," and "connected" should be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
At present, three methods of an electrolysis method, a photodecomposition method and a plasma discharge method are mainly used for preparing hydrogen from water. These three methods are described below, respectively.
(1) Electrolytic method:
currently, water electrolyzed cells are Alkaline Electrolyzers (AECs), proton exchange membrane electrolyzers (PEM) (or solid polymer electrolyte SPE) and Solid Oxide Electrolyzers (SOEC). The purity of the hydrogen obtained by electrolyzing water is high and can reach 99.99 percent.
The electrolysis process produces hydrogen from water, which, because of its extremely low conductivity, cannot be used with pure water and with an electrolyte. In principle, the acidic electrolyte can electrolyze to generate hydrogen and oxygen, but is not generally used because of strong corrosiveness, difficult equipment material selection and manufacturing. In general, alkaline electrolyte, namely KOH or NaOH, is used for preparing hydrogen by water electrolysis.
The reaction type of the electrolyzed water is
An anode of the type @,
@cathode, 2H 2 O+2e - →2OH - +H 2
Total reaction, 2H 2 O→2H 2 +O 2
The cathode of the water electrolysis tank is made of nickel or nickel-plated mild steel or sand-blasted mild steel. In order to obtain pure hydrogen and oxygen while preventing the explosion of the two, the inside of the electrolyzer must be partitioned by a diaphragm.
The structure of the alkaline electrolytic tank is a box type monopole type filter press type bipolar type. The box-type monopolar electrolytic cell has the advantages of simple device, easy maintenance and low component cost, and has the defects of more connected conductors, large ohmic voltage drop on the external circuit, large occupied area, low space-time yield and inapplicability to mass production. The filter press type bipolar electrolytic cell has compact structure, small occupied area, few metal conductors, reduced ohmic voltage of an external circuit and the like, but has more complex structure, slightly large maintenance difficulty, easy electric leakage between two adjacent batteries and easy electrochemical corrosion of points with different polarities generated on the same surface of a polar plate. In addition, the separator is required to have a low resistance value and good mechanical properties, and to effectively prevent gas diffusion, alkali liquid corrosion, and asbestos insulation is often used, but it has carcinogenicity, it directly affects the service life of the electrolytic cell, the separator may be clogged with impurities and the resistance increases, which limits the current density, so it is required to develop a stable alkaline membrane with a high current density, and to increase the service life of the electrolytic cell.
The proton exchange membrane adopts pure water to avoid the corrosion of electrolyte to the tank body, and the safety is higher. Solid polymer ion exchange membranes (proton exchange membranes) are used as electrolytes and function as diaphragms, and solid Nafion perfluorinated sulfonic acid membranes are currently used. The electrode adopts noble metal or oxide thereof with catalytic activity, and the noble metal or oxide thereof is prepared into powder with larger specific area, and the powder is bonded and pressed on two sides of the membrane by using Teflon to form a combination of the membrane and the electrode. The whole electrolytic tank is composed of a plurality of membrane electrode assemblies, and a current collector and an air guide net membrane are arranged in the middle.
When the proton exchange membrane electrolyzer works, water circulates in the anode chamber, oxidation reaction occurs at the anode to generate oxygen, hydrogen ions penetrate through the proton exchange membrane under the action of an electric field to be combined with electrons at the cathode, and reduction reaction occurs to generate hydrogen. The hydrogen ions in the proton exchange membrane are transferred between sulfonic acid groups in the form of hydronium ions to achieve ionic conduction.
The advantages of the proton exchange membrane electrolyzer are high current density, low cell voltage, no solution ohm drop, small bubble effect, etc., however, the main problems are that the technology is complex, the price of the electrode and the proton exchange membrane is very expensive, and if the proton exchange membrane electrolyzer works too high, the solid macromolecule ion exchange membrane can be decomposed to generate toxic gas.
Solid Oxide Electrolytic Cells (SOECs) at high temperatures (800-1000 ℃ C.) water vapor enters from the cathode and is electrolyzed to H 2 Andthrough the electrolyte layer to the anode and release electrons to form O 2 . SOEC has been studied in recent years for its advantages such as high electrolysis efficiency. In the middle of the solid oxide cell is a dense electrolyte layer for separating oxygen and hydrogen and conducting cations and protons, so that the electrolyte structure is required to be dense and possess high ionic conductivity and negligible proton conductivity. The two sides are respectively provided with a porous structure hydrogen electrode and an oxygen electrode which are beneficial to the transmission of hydrogen and oxygen.
Key materials for SOEC include electrolyte, oxygen electrode and hydrogen electrode. Because of the high operating temperature, the structural and chemical stability of the critical materials at high temperatures has a great impact on SOEC performance. Currently, electrolyte materials are mainly classified into ZrO 2 Radical, ceO 2 Base, bi 2 O 3 Radical and ABO 3 Perovskite-like four classes.
In the long-term operation process of the traditional SOEC, delamination easily occurs at the interface of the oxygen electrode and the electrolyte, the activity of the oxygen electrode is reduced, and the performance is greatly attenuated. The biggest problem faced by SOEC is that ceramic-based SOEC is not suitable for operation at high pressures and dynamic power output. Compared with the other two technologies, the maturity is the lowest, and the industrialized application is not realized at present.
(2) Photodecomposition method
In 1972, fujishima et al used single crystal photoelectrodes to decompose water into hydrogen and oxygen under solar drive. The photolytic water is more direct in the way of hydrogen production, so the research of the technology is rapidly becoming a hot spot in the multidisciplinary field.
The electrochemical cell is adopted to electrolyze water, the potential difference is at least greater than 1.23V, but the potential difference is generally greater than 1.8V in practical application, and the water can be decomposed under the light irradiation to be less than 1.23V even without the application of voltage.
The preparation of hydrogen by photocatalytic water splitting is carried out by four ways of photochemical battery, semiconductor photocatalysis, photo-assisted complex catalysis and artificial simulation of photosynthesis water splitting process. The semiconductor photocatalysis is adopted to decompose water to prepare hydrogen, which is the simplest process.
The principle of the method is that when light irradiates the surface of a semiconductor electrode, under the action of light quanta, if the energy of the light quanta is larger than the forbidden band width Eg of the semiconductor, electrons in the valence band will transition to the conduction band, and for n-type semiconductor, holes P are formed in the valence band + The electron donor R in the reduced state in the solution is oxidized after the interface is exceeded: R+P + →R + 。
For p-type semiconductor, then electron e － The electron acceptor O is reduced by crossing the interface as oxidation state: o+e － →O － 。
For example, in TiO 2 (n-type semiconductor) and Pt make up the following cells: (-) n-TiO 2 Aqueous electrolyte solution |pt (+).
When light with proper wavelength irradiates n-TiO 2 Holes can be excited and generated when the electrode is arranged on the electrode:
hv→P + +e －
the electrons are transferred to the Pt cathode along an external line to generate H + And holes P + Oxidation of water across the interface is induced and if in an acidic electrolyte the reaction on the two electrodes can be written as:
@n－TiO 2 anode:
@pt cathode：2H + +2e - →H 2
The total reaction can be written as:
namely, the water is decomposed by the energy of the photons, and the external voltage can be far less than 1.23V due to the intervention of the photons.
Investigation of the photocatalyst shows that the catalyst has d 0 And d 10 Metal ions of electronic configuration, e.g. Ti 4+ 、Zr 4+ 、Ta 5+ 、Nb 5+ 、W 6+ 、Ga 3+ 、In 3+ 、Ge 4+ 、Sn 4+ 、Sn 5+ The oxide, sulfide and nitride semiconductor catalysts of (2) can realize photocatalytic decomposition hydrogen production.
Although there are hundreds of catalysts that meet the conditions for photocatalytic water hydrogen production, the efficiency of photocatalytic hydrogen production is not high. Mainly related to the following factors: the size of the forbidden band width of the semiconductor material determines the range of the semiconductor material capable of absorbing sunlight; the crystalline phase, degree of crystallization, and surface area of the catalyst; the lifetime of the photo-generated electron-hole pairs and the rate at which the redox reaction proceeds at the catalyst surface; the hydrogen and oxygen produce the strength of the water reverse reaction.
The current yield of photocatalytic hydrogen production is a great distance from actual industrialization. The industrial standard of hydrogen production by solar photocatalytic water splitting is that the catalyst can utilize sunlight with the wavelength below 600nm, the quantum efficiency is more than 30%, the service life of the catalyst is more than 1 year, and the quantum efficiency of the catalyst is at least 10%. It is considered by scholars that if the quantum efficiency of solar spectrum is up to 5%, the hydrogen produced by this method will be cheaper than other methods. In fact, the quantum efficiency achieved by photolysis of water is only about 0.2%.
(3) Plasma discharge method:
the plasma is a fourth state of matter other than solids, liquids, and gases. The gas-like substance is an ionized gas-like substance composed of positive and negative ions generated after the atoms and atomic groups of which partial electrons are deprived are ionized. Plasma discharge has also been studied for separating water to produce hydrogen.
At present, low-temperature plasma which is more studied and is considered to have application prospect is Dielectric Barrier Discharge (DBD). In a DBD-corona hybrid reactor with glass as the barrier medium, rehman f. Et al, plasma discharge of water vapor (and argon) at atmospheric pressure and small electrode spacing separated hydrogen with energy and thermodynamic efficiencies of 78.8% and 79.2%, respectively. However, the heat of vaporization of water is not counted. The existence of argon gas makes the decomposition speed twice as high as that of original argon gas, and the electrons collide with argon atoms to generate excited Ar 3 P) which collide with water molecules resulting in a more efficient dissociation excitation to generate additional OH radicals. It is known that adding argon increases the decomposition rate, but also increases the cost of hydrogen production. In addition, the surface properties of the glass, such as contact angle, are significantly changed after plasma treatment. The influence of air cooling and quenching, water content, total gas flow, working electrode material and porous working electrode when hydrogen production is performed by DBD water splitting is studied by Li W.P. The feeding condition is 300cm 3 H at a volume ratio of 3% 2 O/Ar achieves the best water splitting performance under the applied voltage with the frequency of 17.3kHz and the voltage of 6.93 kVp-p. Due to the large surface area of the copper mesh and the narrowing of the discharge gas, the water decomposition performance, especially the energy efficiency, is improved. The porous working electrode consisting of stainless steel bars and copper mesh has the best comprehensive performance, the hydrogen yield is 7.09%, and the energy efficiency is 0.68% [16] . Varne, M.et al report a similar conversion of water vapor to hydrogen in DBD in argon and mention is made of activated silica gel/silica gel and molecular sieve treated Ar, resulting in a difference in hydrogen yield. Dey g.r. et al also reported the conversion of water vapor to hydrogen in argon using DBD cold plasma, discussing the effects of electrode materials, applied voltages, and blocking dielectrics.
El-Shafie M. Et al also decomposed water vapor at 573K to hydrogen and oxygen using DBD plasma, and obtained maximum mole fractions of hydrogen, hydrogen flow and conversion of 2.3%, 9.42g/h and 42.51%, respectively, with maximum thermal efficiencies of 49.32% without the use of a carrier gas.
Kierzkowska-Pawlak, H.et al studied a method of water splitting by focusing a femtosecond laser pulse (100 fs, λ=800 nm) into a quartz bath containing ultrapure water. The laser can not directly ionize water in the infrared band, so that water molecules in the focusing region can be ionized only by absorbing a plurality of photons (the author assumes that the ionization energy of the water is 8 eV) to form plasma, and then the water is decomposed into H 2 And H 2 O 2 . From this, the femtosecond laser pulse is used for cracking water to produce hydrogen, and proper irradiation conditions such as light intensity are needed, otherwise sunlight can be directly used for producing hydrogen by water. In addition, the laser also drives the generated negative ions to consume energy. Further, the current efficiency of the laser is about 55% at maximum, excluding losses of the laser during transmission.
Lytle s et al studied, analyzed and simulated plasma hydrogen production with 2.45GHz microwaves. The 2-dimensional value simulation is performed by using a COMSOL Multiphysics plasma and electromagnetic wave module, and the hydrogen peroxide are separated from each other by microwave discharge of water vapor, assuming that the inner wall of the glass container is a perfect conductor and a discharge gap is formed between tungsten sharp electrodes extending into the container. The study illustrates the separation of H from water vapor by microwave discharge 2 However, electromagnetic interference and pollution of microwaves to the periphery during actual large-scale application are not considered, whether a microwave source can achieve required voltage, current and power is not considered, the relative dielectric constant of water is 82 actually, and a discharge gap forms a capacitor with a large capacitance value during high-concentration water vapor, so that displacement current is very large.
The invention is described in further detail below with reference to the attached drawing figures:
referring to fig. 4, an embodiment of the present invention discloses an apparatus for preparing hydrogen and oxygen by electron irradiation of liquid water, comprising an electron source chamber 16 and a reaction chamber 17, which are isolated by a high melting point metal film 18.
A cathode 19, an insulating core transformer and rectifier filter 20, an accelerator 21, and a metal film 18 as an anode are provided in the electron source chamber 16; the insulation core transformer and the rectifying filter 20 are connected with the low-voltage alternating-current power supply 22, and the accelerator 21 is powered after the voltage of the low-voltage alternating-current power supply 22 is boosted, rectified and filtered; the cathode 19 is of an indirect type and is made of lanthanum hexaboride material, and emits electron beams under a strong electric field between the high-temperature cathode 19 and the accelerator 21, and the electron beams penetrate through the metal film 18 and enter the reaction chamber 17 after being accelerated by the accelerator 21; a vacuum system 42 is also connected to the electron source chamber 16 for maintaining a vacuum level within the electron source chamber 16.
A gas collecting cathode 23, a gas collecting anode 24, a hydrogen separation chamber 25 and an oxygen separation chamber 26 are arranged in the reaction chamber 17, and the gas collecting cathode 23 and the gas collecting anode 24 are connected with the anode and the cathode of the direct current power supply DC 1; the outlet of the hydrogen separation chamber 25 is connected with a hydrogen collection system, the hydrogen collection system comprises a first compressor 27 and a hydrogen tank 28 connected to the outlet of the first compressor 27, and the inlet pipeline of the first compressor 27 is also connected with a hydrogen detection chamber 29; the outlet of the oxygen separation chamber 26 is connected with an oxygen collection system, the oxygen collection system comprises a second compressor 30 and an oxygen tank 31 connected to the outlet of the second compressor 30, and an inlet pipeline of the second compressor 30 is also connected with an oxygen detection chamber 32; the electron beam bombarded liquid water transmitted from the metal film 18 generates hydrogen gas, hydrogen ions, oxygen gas, oxygen ions, and other species; the gas collecting cathode 23 and the gas collecting anode 24 are electrified to form an electrostatic field, so that positive ions such as hydrogen ions move to the gas collecting cathode to obtain electrons to form hydrogen, and negative ions such as oxygen ions move to the gas collecting anode to release electrons to form oxygen; and finally separating the hydrogen and the oxygen from the mixed gas.
The reaction chamber 17 is provided with a water inlet 33 and a water outlet 40, the water inlet 33 is sequentially connected with a first water valve 34, a first water pump 35 and a water reservoir 36, and an inlet of the water reservoir 36 is connected with the water outlet 40 of the reaction chamber 17. The reservoir 36 is provided with a water replenishment port 37, and the water replenishment port 37 is sequentially connected with a second water valve 41, a second water pump 38 and a reservoir 39.
The invention also discloses a method for preparing hydrogen and oxygen by electron irradiation of liquid water, which comprises the following steps:
step 1, the vacuum system 42 is powered on to operate, and the electron source chamber 16 is pumped to an ultra-high vacuum state.
And 2, opening a water valve, starting a water pump, and enabling water to circulate through the reaction chamber 17.
And 3, switching on a direct current power supply DC1, and forming an electrostatic field by a gas collecting anode 24 and a gas collecting cathode 23 of the reaction chamber 17.
Step 4, switching on a low-voltage alternating current power supply 22, boosting, rectifying and filtering by an insulating core transformer and a rectifying filter 20 of the electron source chamber 16, supplying power to an accelerator 21, heating an indirectly heated cathode 19 made of lanthanum hexaboride material, and emitting electron beams under a strong electric field between the high-temperature cathode 19 and the accelerator 21; the electron beam is accelerated by the accelerator 21 and then penetrates the metal film 18 to enter the reaction chamber 17.
Step 5, the liquid water transmitted into the electron beam bombardment reaction chamber 17 generates substances such as hydrogen, hydrogen ions, oxygen ions and the like; the electrostatic field between the gas collecting cathode 23 and the gas collecting anode 24 enables positive ions such as hydrogen ions to move to the gas collecting cathode to obtain electrons so as to form hydrogen, and enables negative ions such as oxygen ions to move to the gas collecting anode to release electrons so as to form oxygen; the hydrogen separation chamber 25 and the oxygen separation chamber 26 separate hydrogen and oxygen from the mixed gas, respectively.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. An apparatus for preparing hydrogen and oxygen by electron irradiation of liquid water, comprising:
an electron source chamber (16), wherein a cathode (19) is arranged in the electron source chamber (16); the electron source chamber (16) is arranged on the reaction chamber (17) and is communicated with the reaction chamber (17) through the metal film (18); an accelerator (21) for accelerating electrons is provided between the cathode (19) and the metal film (18) serving as the anode; the cathode (19) and the accelerator (21) are connected with a low-voltage alternating current power supply (22); the cathode (19) is connected with the accelerator (21) through an insulating core transformer and a rectifying filter (20) and is connected with a low-voltage alternating current power supply (22), the accelerator is powered by the insulating core transformer and the rectifying filter after boosting, rectifying and filtering, the cathode is heated, and an electron beam is emitted under a strong electric field between the high-temperature cathode and the accelerator; the insulating core transformer and the rectifying filter (20) are arranged in the electron source chamber (16), and the low-voltage alternating current power supply (22) is arranged outside the electron source chamber (16);
a reaction chamber (17), wherein a gas collecting cathode (23), a gas collecting anode (24), a hydrogen separation chamber (25) and an oxygen separation chamber (26) are arranged in the reaction chamber (17); the gas collecting anode (24) and the gas collecting cathode (23) are respectively connected to the positive electrode and the negative electrode of the direct current power supply (DC 1); the hydrogen separation chamber (25) is arranged above the gas collecting cathode (23), and the oxygen separation chamber (26) is arranged above the gas collecting anode (24); the hydrogen separation chamber (25) and the oxygen separation chamber (26) are respectively connected with a hydrogen collection system and an oxygen collection system.
2. Device for the preparation of hydrogen and oxygen by electron irradiation of liquid water according to claim 1, characterized in that the cathode (19) is of the indirect type and is made of lanthanum hexaboride.
3. The apparatus for preparing hydrogen and oxygen by irradiating liquid water with electrons according to claim 1, wherein a vacuum system (42) is further connected to the electron source chamber (16) for maintaining the vacuum degree in the electron source chamber (16).
4. The apparatus for preparing hydrogen and oxygen by electron irradiation of liquid water according to claim 1, wherein the hydrogen collecting system comprises a first compressor (27), and a hydrogen tank (28) connected at the outlet of the first compressor (27), and a hydrogen detecting chamber (29) is further connected to the inlet pipe of the first compressor (27).
5. The apparatus for preparing hydrogen and oxygen by electron irradiation of liquid water according to claim 1 or 4, wherein the oxygen collection system comprises a second compressor (30), and an oxygen tank (31) connected at the outlet of the second compressor (30), and an oxygen detection chamber (32) is further connected to the inlet pipe of the second compressor (30).
6. The device for preparing hydrogen and oxygen by electron irradiation of liquid water according to claim 1, wherein the reaction chamber (17) is provided with a water inlet (33) and a water outlet (40), the water inlet (33) is sequentially connected with a first water valve (34), a first water pump (35) and a water reservoir (36), and an inlet of the water reservoir (36) is connected with the water outlet (40) of the reaction chamber (17).
7. The device for preparing hydrogen and oxygen by using the electron irradiation liquid water according to claim 6, wherein the water reservoir (36) is provided with a water supplementing port (37), and the water supplementing port (37) is sequentially connected with a second water valve (41), a second water pump (38) and a water reservoir (39).
8. A method for producing hydrogen and oxygen by electron irradiation of liquid water using the apparatus according to any one of claims 1 to 7, comprising the steps of:
step 1, starting a power supply of a vacuum system (42), and pumping an electron source chamber (16) to an ultrahigh vacuum state;
step 2, a first water valve (34) is opened, a first water pump (35) is started, and water circulates through the reaction chamber (17);
step 3, a direct current power supply (DC 1) is started, and a gas collecting anode (24) and a gas collecting cathode (23) of the reaction chamber (17) form an electrostatic field;
step 4, a low-voltage alternating current power supply (22) is started, the accelerator (21) is powered after boosting, rectifying and filtering through an insulating core transformer and a rectifying filter (20), the cathode (19) is heated, and an electron beam is emitted under a strong electric field between the high-temperature cathode (19) and the accelerator (21); the electron beam penetrates through the metal film (18) to enter the reaction chamber (17) after being accelerated by the accelerator (21);
step 5, the liquid water transmitted into the electron beam bombardment reaction chamber (17) generates hydrogen, hydrogen ions, oxygen and oxygen ions; an electrostatic field between the gas collecting cathode (23) and the gas collecting anode (24) enables hydrogen ions to move to the gas collecting cathode to obtain electrons so as to form hydrogen, and enables oxygen ions to move to the gas collecting anode to release electrons so as to form oxygen; the hydrogen separation chamber (25) and the oxygen separation chamber (26) separate hydrogen and oxygen from the mixed gas, respectively.
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